Certain n, n&#39;-disubstituted ethylenebisbenzothiazolesulfenamides



United States Patent CERTAIN N,N'-DISUBSTITUTED ETHYLENEBIS- BENZOTHIAZOLESULFENAMIDES Norman K. Sundholm, Middlebury, Conn., assignor to United States Rubber Company, New York, N.Y., a corporation of New Jersey No Drawing. Application May 15, 1958 Serial No. 735,373

5 Claims. (Cl. 260-788) This invention relates to new compositions of matter which are useful as accelerators for the vulcanization of rubber and other vulcanizable rubberlike substances. Further, they have the useful property of showing good resistance to scorch, that is, they have little tendency to cause incipient vulcanization of conventional rubber stocks during processing.

This application is a continuation-in-part of my application Serial No. 636,883, filed January 29, 1957, now abandoned.

When a rubber stock, including vulcanizing agent, accelerator, and other compounding ingredients, is mixed and shaped, said stock is at an elevatedtemperature, usually in the 240 .F.2'70 F. range. Depending upon thenature of the rubber, the compounding ingredients, and the temperature, undesired vulcanization may take place. This is a serious problem because the partially vulcanized rubber stock is no longer plastic and cannot be shaped into the desired form. The partially vulcanized (scorched) stock may in certain cases be reworked for further use, but this is a time-consuming and an extra-cost practice. If the vulcanization has gone too far, the stock must be scrapped, resulting in an economic loss.

The scorch problem has become of increasing acuteness in the rubber industry due principally to the increased use of the activating furnace blacks as reinforcing agents and the employment of higher processing temperatures resulting from increased productivity. This problem has been solved to a large extent by the application of accelerators having more delayed action than Z-mercaptobenzothiazole and benzothiazolyl disulfide, but there is need for further improvement.

It is an object of this invention to provide new compositions of matter which are useful as accelerators for the vulcanization of rubber and other vulcanizable rubberlike substances, and which show especially good resistance to scorch. It is a further object to provide a method for vulcanizing sulfur-vulcanizable rubbers in the presence of said new compositions of matter. Other objects will appear from the description of the invention which follows.

The new accelerators of this invention comprise the N,N' ethylenebis( N substituted 2 benzothiazolesulfenamides) represented by the structural formula where R is a member of the group consisting of isopropyl, tert-butyl, and cyclohexyl radicals, the two Rs being alike.

In US. Patent No. 2,339,552, which issued on January 18, 1944, to Edward L. Carr, the preparation and accelerating properties of the unsubstituted compound, that is, where R is hydrogen in the above formula, are reported. It will be shown below that the new accelerators of this invention have markedly more delayed action than the accelerator of the Carr reference and therefore can be used as accelerators in scorchy rubber stocks in which Carrs compound could be used only with difficulty.

The new accelerators are readily prepared by the reaction of two moles of 2-benzothiazolesulfenyl chloride with one mole of the corresponding N,N'-disubstituted ethylenediamine in the presence of two moles of an aliphatic tertiary amine such as triethylamine according to the equation The 2-benzothiazolesulfenyl chloride used is prepared by the chlorination of benzothiazolyl disulfide in a suitable organic solvent according to US. Patent No. 2,257,974, which issued to William E. Messer on October 7, 1941. The N,N'-disubstituted ethylenediamines are prepared by the reaction of an excess of the corresponding primary amine with ethylene bromide using the procedure of W. R. Boon, Journal of the Chemical Society, 1947, 307.

The preparation and properties of the new accelerators are as follows:

Example 1 .-N,N-ethylenebis(N-isopropyl Z-benzothiazolesulfenamide) A solution of 2-benzothiazolesulfenyl chloride was prepared by the treatment of a stirred suspension of 68 grams of technical benzothiazolyl disulfide in 500 ml. of anhydrous ethylene chloride with 14.5 grams of chlorine. This solution was added dropwise to a stirred solution of 28.8 grams of N,N-diisopropylethylenediamine and 42.4 grams of triethylamine in ml. of anhydrous ethylene chloride during 70 minutes. The temperature of the reaction mixture was kept at 18 C.-22 C. during the addition. After one-half hour of stirring following completion of the addition, the mixture was filtered and the triethylamine hydrochloride was washed with two 100-ml. portions of ethylene chloride. The wash was added to the filtrate and the ethylene chloride was removed. The residual product was purified by recrystallization from ethanol using decolorizing carbon to give colorless crystals melting at 137 C.- 137.5 C.

Analysis.Calculated for C H N S Found: N, 11.75.

The remaining accelerators were above procedure.

prepared using the Example 2.N,N'-ethylenebis(N-tert butyl-Z-benzothiazolesulfenamde) Example 3.N,N'-ethylenebis(N-cyclohexyl-Z-benzothiazolesulfenamide) This compound, prepared from N,N-dicyclohexylethylenediamine, 2-benzothiazolesulfenyl chloride, and tri- Parts by weight Smoked sheet 100 Furnace black 45 Zinc oxide Zinc salts of cocoanut oil acids 3.5 Pine tar 3.5 Antioxidant 1 2.0 Sulfur 2.25 Accelerator 0.5

Equal parts of BLE (an acetone-diphenylamine condensate) and Flexamine (a mixture of diphenyl-p-phenylenediamine and the reaction product of formaldehyde and BLE).

Stocks were compounded containing as the accelerator the following:

Accelerator 2-Mercaptobenzothiazole.

Benzothiazolyl disulfide.

N ,N '-Ethylenebis(2-benzothiazolesulfenamide). N ,N-Et-hylenebis(N-methyl-2-beuzothiazolesulfenamide) N,N-E thylenebis( N-ethyl-Z-benzbthiaz olesulienarm'de) N,N-E thy1enebis(N-isopropyl-Z-b enzothiazolesulienamide) N,N-E thylenebis (N-tert-butyl-2-b enzothiaz olesulfeuamide) N,N-E thylenebis (N-cyclohexyl-Z-h enzothiazolesulfenamide) The stocks were cured by heating in a press at 274 F. using curing times of 30 and 90 minutes. The physical properties of the respective stocks at the respective curing times are given in the following table.

Cure 300% Tensile Elongation Stock Time, Modulus, Strength, at Break,

min. p.s.i p.s.i. percent These data show that the new compositions of matter are good accelerators.

' In order to demonstrate the scorch resistance of the new accelerators, the Mooney scorch times of these stocks were determined on the Mooney viscometer at 250 F. (per ASTM Method D1077-55T). The scorch time was measured from the time the viscometer was closed until the viscosity had increased three points above the minimum reading; the small rotor was used in obtaining the following data.

The scorch times show that the new accelerators (contained in stocks F, G, and H) have markedly superior delayed action compared to Carrs unsubstituted compound, the methyl and ethyl derivatives thereof, Z-mercaptobenzothiazole, and benzothiazolyl disulfide, since mcmrnoouw the longer the scorch time the greater the delayed action butadiene with styreneor acrylonitrile.

of the accelerator. The difference in favor of the accelerators of this invention is represented by a factor on the order of percent. Because of this large improvement in delayed action, the new accelerators will permit the user to process his rubber stocks at higher temperatures and, therefore, to process more compounded rubher in a given length of time than if Carrs accelerator or another of the tested accelerators is used.

The new accelerators may be used to accelerate the vulcanization of any of the natural or synthetic rubbers which ordinarily lend themselves to cure with sulfur or other curing agent susceptible to acceleration, and which include among others the prominent rubbery polymers derived from 1,3-butadiene, such as copolymers of Polybutadiene and polyisoprene rubbers and copolymers of isobutylene and a diolefin are other examples.

The new accelerators may be used in combination with other compounding ingredients than the ones shown here. These include acceleration activators and retarders, other reinforcing agents, softeners, antioxidants, and the like to produce various types of rubber compounds.

, Having thus described my invention, what I claim and desire to protect by Letters Patent is:

1. Compounds represented by the structural formula References Cited in the file of this patent 1 UNITED STATES PATENTS 2,050,198 'Sebrell Aug. 4, 1936 2,382,793 Howland Aug. 14, 1945 2,762,814 Lunt Sept. 11, 1956 2,766,237 DAmico Oct. 9, 1 956 2,776,297 Cherlow et a1 Jan. 1, 1957 I r FOREIGN PATENTS 42,597

Great Britain Sept. 6, 1950 

1. COMPOUNDS REPRESENTED BY THE STRUCTURAL FORMULA
 5. A METHOD OF VULCANIZING SULFUR-VULCANIZABLE RUBBERS WHICH COMPRISES VULCANIZING THE SAME IN THE PRESENCE OF A COMPOUND AS SET FORTH IN CLAIM
 1. 